Surfactant-containing formulations

ABSTRACT

The invention relates to surfactant-containing formulations which comprise, as surfactant, an N-(3-dialkylamino)propyl-N-polyhydroxyalkylcarboxamide of the formula                    
     where R is an aliphatic radical having from 8 to 24 carbon atoms, R 1  and R 2 , which are identical or different, are alkyl groups having from 1 to 4 carbon atoms or hydroxyalkyl groups having from 2 to 4 carbon atoms, and Z is a linear polyhydroxyhydrocarbon radical having at least 3 OH groups, which may also be alkoxylated, and also to their acid addition products. The surfactant-containing formulations are used in industrial and standard household surfactant compositions.

BACKGROUND OF THE INVENTION

The use of fatty acid N-alkylpolyhydroxyalkylamides and, in particular,of fatty acid N-methylglucamide is already known from DE-A-4 430 085;DE-A-4 326 950; DE-A-4 432 366; DE-A-4 424 823; WO 92/6153; WO 92/6156;WO 92/6157; WO 92/6158; WO 92/6159 and WO 92/6160. As well as their highdetergency, important advantages of the fatty acid N-methylglucamidesare their good biodegradability and the fact that they can be preparedfrom renewable raw materials. The use of this group of substances asthickeners is also known (EP-A-285 768).

A disadvantage for the use and formulation is the limited solubility ofthese substances, particularly those having a chain length greater thanC16. At relatively high concentrations in water they can only be handledwith difficulty because of their high viscosity. Relatively hightemperatures, which reduce the viscosity, however, lead to increasedhydrolysis.

DE-A-4 238 207 and DE-A-4 238 211 disclose the use of fatty acidpolyhydroxyalkylamides as surfactants, which differ from the previouslymentioned fatty acid N-alkylpolyhydroxyalkylamides by virtue of the factthat the alkyl group is substituted by a dialkylamino group.Furthermore, these sugar surfactants are quaternized.

SUMMARY OF THE INVENTION

It has now been found that the sugar surfactants described in DE-A-4 238207 and DE-A-4 238 211 are also excellent surfactants in theirnonquaternized form. This finding is surprising since the cited priorart makes no mention of the use of the nonquaternized compounds of thistype as surfactants.

The invention provides surfactant-containing formulations whichcomprise, as surfactant, anN-(3-dialkylamino)propyl-N-polyhydroxyalkylcarboxamide of the formula

where R is an aliphatic radical having from 8 to 24 carbon atoms, R¹ andR², which are identical or different, are alkyl groups having from 1 to4 carbon atoms or hydroxyalkyl groups having from 2 to 4 carbon atoms,and Z is a linear polyhydroxyhydrocarbon radical having at least 3 OHgroups, which may also be alkoxylated, and also their acid additionproducts.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preference is given to compounds of the formula 1 in which R¹ and R² aremethyl, and Z is the residue of a sugar alcohol derived from a reducingmono- or disaccharide, in particular from glucose.

These compounds are prepared as stated in DE-A-19 51 2249 by acylatingan amine of the formula (2)

Z—NH—(CH₂)₃—NR¹R²  (2)

with introduction of the radical R—CO, where R, R¹, R² and Z are asdefined above.

The acid addition products are then obtained in an additional step byadding a suitable acid. Examples of such acids are mineral acids, suchas hydrochloric acid, or organic acids, such as carboxylic acids (aceticacid), hydroxycarboxylic acids (lactic acid), branched, linear,saturated or unsaturated fatty acids, dicarboxylic acids (maleic acid,succinic acid, adipic acid), polycarboxylic acids (citric acid) or aminoacids and derivatives thereof.

Compared with the non-basically substituted known compounds, thesecompounds have the added advantage that, for matching the hydrophilicproperties, not only is the radical Z available, but also the basicallysubstituted alkylene radical, and so the hydrophilic properties can bebetter tailored than the hydrophobic properties—effected by means of theradical R. The compounds of the formula 1 and their acid additionproducts are generally suitable as surfactants since they have excellentsurfactant properties, such as very good foaming ability, good fatdispersibility (soil titration) and good detergency, coupled with highstability to water hardness and good skin compatibility.

They are suitable for all types of surfactant-containing formulations,in particular for cosmetic cleansing formulations and householdcleaners. The formulations according to the invention preferablycomprise the compounds of the formula l in an amount of from 0.1 to 99%by weight, in particular from 1 to 50% by weight.

Preferred formulations according to the invention are pulverulentuniversal detergents (from 1 to 30% by weight), liquid universaldetergents (from 1 to 70% by weight), liquid light-duty detergents (from1 to 50% by weight), hand modifiers (from 1 to 50% by weight), manualdishwashing compositions (from 1 to 50% by weight), toilet cleaners(from 1 to 50% by weight), liquid cleaners and disinfectants (from 1 to30% by weight), bar soaps of the combination bar type (from 1 to 2% byweight), syndet soaps (from 1 to 2% by weight), hair shampoos (from 1 to30% by weight), hair rinses (from 1 to 30% by weight), hair dyes (from 1to 30% by weight), hair-waving compositions (from 1 to 30% by weight),foam baths (from 1 to 30% by weight), face cleansers (from 1 to 30% byweight), textile and fiber auxiliaries (from 1 to 30% by weight),leather greasing agents (from 1 to 30% by weight), flotation auxiliaries(from 1 to 30% by weight) and auxiliaries for dewatering sludges. Thepercentages in brackets indicate the preferred content of surfactant ofthe formula 1 in these formulations.

The formulations according to the invention may comprise a compound ofthe formula 1 or their acid addition products as the sole surfactant,but these surfactants are preferably combined with other customaryanionic, nonionic, cationic and/or amphoteric surfactants. The mixingratio between the surfactants of the formula 1 or their acid additionproducts and the other surfactants can fluctuate within wide limits, forexample in the weight ratio from 1 to 99 to 99 to 1, preferably from 80to 20 to 20 to 80. The total concentration of surfactants in theformulations according to the invention can be from 1 to 99% by weight,preferably from 5 to 50% by weight.

Suitable anionic surfactants include sulfonates, sulfates, carboxylates,phosphates and mixtures of the above compounds. Suitable cations in thiscase are alkali metals such as, for example, sodium or potassium, oralkaline earth metals such as, for example, calcium or magnesium, andammonium, substituted ammonium compounds, including mono-, di- ortriethanolammonium cations and mixtures of the cations. The followingtypes of anionic surfactants are of particular interest: alkyl estersulfonates, alkylsulfates, alkyl ether sulfates, alkylbenzenesulfonates,secondary alkanesulfonates and soaps as described below.

Alkyl ester sulfonates include linear esters of C₈-C₂₀-carboxylic acids(i.e. fatty acids) which are sulfonated using gaseous SO₃, as describedin The Journal of the American Oil Chemists' Society 52 (1975), pp.323-329. Suitable starting materials are natural fats such as, forexample, tallow, palm oil or coconut oil, but they can also besynthetic. Preferred alkyl ester sulfonates, particularly for detergentapplications, are compounds of the formula

where R¹ is a C₈-C₂₀-hydrocarbon radical, preferably alkyl, and R is aC₁-C₆-hydrocarbon radical, preferably alkyl. M is a cation which forms awater-soluble salt with the alkyl ester sulfonate. Suitable cations aresodium, potassium, lithium or ammonium cations, such asmonoethanolamine, diethanolamine and triethanolamine. R¹ is preferablyC₁₀-C₁₆-alkyl and R is preferably methyl, ethyl or isopropyl. Particularpreference is given to methyl ester sulfonates where R ¹isC₁₀-C₁₆-alkyl.

Alkylsulfates are in this case water-soluble salts or acids of theformula ROSO₃M, where R is preferably a C₁₀-C₂₄-hydrocarbon radical,preferably C₁₀-C₂₀-alkyl or hydroxyalkyl, particularly preferablyC₁₂-C₁₈-alkyl or -hydroxyalkyl. M is hydrogen or a cation, e.g. analkali metal cation (e.g. sodium, potassium, lithium), ammonium orsubstituted ammonium, e.g. methyl-, dimethyl- and trimethylammoniumcations and quaternary ammonium cations, such as tetramethylammonium anddimethylpiperidinium cations and quaternary ammonium cations, derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine andmixtures thereof. Alkyl chains with C₁₂-C₁₆ are preferred for low washtemperatures (e.g. below about 50° C.) and alkyl chains with C₁₆-C₁₈ arepreferred for higher wash temperatures (e.g. above about 50° C.).

Alkyl ether sulfates are water-soluble salts or acids of the formulaRO(A)_(m)SO₃M, where R is an unsubstituted C₁₀-C₂₄-alkyl or hydroxyalkylradical, preferably a C₁₂-C₂₀-alkyl or hydroxyalkyl radical,particularly preferably C₁₂-C₁₈-alkyl or -hydroxyalkyl radical. A is anethoxy or propoxy unit, m is a number greater than 0, preferably betweenabout 0.5 and about 6, particularly preferably between about 0.5 andabout 3, and M is a hydrogen atom or a cation such as, for example,sodium, potassium, lithium, calcium, magnesium, ammonium or asubstituted ammonium cation. Specific examples of substituted ammoniumcations are methyl-, dimethyl-, trimethylammonium and quaternaryammonium cations such as tetramethylammonium and dimethylpiperidiniumcations, and those which are derived from alkylamines, such asethylamine, diethylamine, triethylamine and mixtures thereof. Exampleswhich may be given are C₁₂-C₁₈ fatty alcohol ether sulfates where thecontent of ethylene oxide is 1, 2, 2.5, 3 or 4 mol per mole of fattyalcohol ether sulfate, and where M is sodium or potassium.

In secondary alkanesulfonates, the alkyl group can either be saturatedor unsaturated, branched or linear and may be substituted by a hydroxylgroup. The sulfo group can occupy any position over the whole carbonchain, except that the primary methyl groups at the start and end of thechain have no sulfo groups. The preferred secondary alkanesulfonatescontain linear alkyl chains having from about 9 to 25 carbon atoms,preferably from about 10 to about 20 carbon atoms and particularlypreferably from about 13 to 17 carbon atoms. Examples of the preferredcation are sodium, potassium, ammonium, mono-, di- ortriethanolammonium, calcium or magnesium.

Other suitable anionic surfactants are alkenyl- oralkylbenzenesulfonates. The alkenyl or alkyl group can be branched orlinear and may be substituted by a hydroxyl group. The preferredalkylbenzenesulfonates contain linear alkyl chains having from about 9to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms,and the cation is sodium, potassium, ammonium, mono-, di- ortriethanolammonium, calcium or magnesium and mixtures thereof. For mildsurfactant systems, magnesium is the preferred cation while sodium ispreferred for standard washing applications. The same applies toalkenylbenzenesulfonates.

The term anionic surfactants also includes olefinsulfonates, which areobtained by sulfonation of C₁₂-C₂₄-, preferably C₁₄-C₁₆-α-olefins withsulfur trioxide and subsequent neutralization. Owing to the preparationprocess, these olefinsulfonates may contain relatively small amounts ofhydroxyalkanesulfonates and alkanedisulfonates. Specific mixtures ofα-olefin sulfonates are described in U.S. Pat. No. 3,332,880.

Further preferred anionic surfactants are carboxylates, for examplefatty acid soaps and comparable surfactants. The soaps can be saturatedor unsaturated and can contain various substituents, such as hydroxylgroups or α-sulfonate groups. Preference is given to linear saturated orunsaturated hydrocarbon radicals having from about 6 to about 30 carbonatoms, preferably from about 10 to about 18 carbon atoms.

Other suitable anionic surfactants are salts of acylaminocarboxylicacids, the acyl sarcosinates obtained by reacting fatty acid chlorideswith sodium sarcosinate in an alkaline medium; fatty acid-proteincondensation products obtained by reacting fatty acid chlorides witholigopeptides; salts of alkylsulfamidocarboxylic acids, salts of alkyland alkylaryl ether carboxylic acids, C₈-C₂₄-olefinsulfonates,sulfonated polycarboxylic acids prepared by sulfonation of the pyrolysisproducts of alkaline earth metal citrates, as described for example inGB-1,082,179; alkyl glycerol sulfates, fatty acyl glycerol sulfates,alkylphenol ether sulfates, primary paraffinsulfonates, alkylphosphates,alkyl ether phosphates, isethionates, such as acylisethionates,N-acyltaurides, alkylsuccinates, sulfosuccinates, monoesters ofsulfosuccinates (particularly saturated and unsaturatedC₁₂-C₁₈-monoesters) and diesters of sulfosuccinates (particularlysaturated and unsaturated C₁₂-C₁₈-diesters), acylsarcosinates, sulfatesof alkylpolysaccharides such as sulfates of alkylpolyglycosides,branched primary alkylsulfates and alkylpolyethoxycarboxylates such asthose of the formula RO(CH₂CH₂)_(k)CH₂COO⁻M⁺, where R is C₈-C₂₂-alkyl, kis a number from 0 to 10 and M is a cation, resin acids or hydrogenatedresin acids, such as rosin or hydrogenated rosin or tall oil resins andtall oil resin acids.

Further examples are described in Surface Active Agents and Detergents(Vol. I and II, Schwartz, Perry and Berch).

Examples of suitable nonionic surfactants are the following:

Polyethylene, polypropylene and polybutylene oxide condensates ofalkylphenols.

These compounds comprise the condensation products of alkylphenolshaving a C₆-C₂₀-alkyl group, which can be either linear or branched,with alkene oxides. Preference is given to compounds containing about 5to 25 mol of ethylene oxide per mole of alkylphenol. Commerciallyavailable surfactants of this type are, for example, Igepal® CO-630,Triton® X-45, X-114, X-100 and X102, and the ®Arkopal-N products fromHoechst AG.

Condensation products of aliphatic alcohols with from about 1 to about25 mol of ethylene oxide.

The alkyl chain of the aliphatic alcohols can be linear or branched,primary or secondary, and generally contains from about 8 to about 22carbon atoms. Particular preference is given to the condensationproducts of C₁₀-C₂₀-alcohols with from about 2 to about 18 mol ofethylene oxide per mole of alcohol. The alkyl chain can be saturated orunsaturated. The alcohol ethoxylates can have a narrow (“narrow rangeethoxylates”) or a broad (“broad range ethoxylates”) homologdistribution of the ethylene oxide. Examples of commercially availablenonionic surfactants of this type are Teritol® 15-S-9 (condensationproduct of a C₁₁-C₁₅ linear secondary alcohol with 9 mol of ethyleneoxide), Tergitol® 24-L-NMW (condensation product of a C₁₂-C₁₄ linearprimary alcohol containing 6 mol of ethylene oxide, having a narrowmolecular weight distribution). This product class also includes theGenapol® products from Hoechst AG.

Condensation products of ethylene oxide with a hydrophobic base, formedby condensation of propylene oxide with propylene glycol.

The hydrophobic part of these compounds preferably has a molecularweight of between about 1500 and about 1800. The addition of ethyleneoxide to this hydrophobic part leads to an improvement in the solubilityin water. The product is liquid up to a polyoxyethylene content of about50% of the total weight of the condensation product, which correspondsto a condensation with up to about 40 mol of ethylene oxide.Commercially available examples of this product class are the Pluronic®products from BASF and the ®Genapol PF products from Hoechst AG.

Condensation product of ethylene oxide with a reaction product ofpropylene oxide and ethylenediamine.

The hydrophobic unit of these compounds consists of the reaction productof ethylenediamine with excess propylene oxide and generally has amolecular weight of from about 2500 to about 3000. Ethylene oxide isadded onto this hydrophobic unit until the product has a content of fromabout 40 to about 80% by weight of polyoxyethylene and a molecularweight of from about 5000 to about 11000. Commercially availableexamples of this compound class are the ®Tetronic products from BASF andthe ®Genapol PN products from Hoechst AG.

Semipolar Nonionic Surfactants

This special category of nonionic compounds includes water-soluble amineoxides, water-soluble phosphine oxides and water-soluble sulfoxides,each having an alkyl radical of from about 10 to about 18 carbon atoms.Semipolar nonionic surfactants are also amine oxides of the formula

where R is an alkyl, hydroxyalkyl or alkylphenol group each having fromabout 8 to about 22 carbon atoms, R² is an alkylene or hydroxyalkylenegroup having from about 2 to 3 carbon atoms or mixtures thereof, eachradical R¹ is an alkyl or hydroxyalkyl group having from about 1 toabout 3 carbon atoms or a polyethylene oxide group having from about 1to about 3 ethylene oxide units. The R¹ groups can be linked to oneanother via an oxygen or nitrogen atom and can therefore form a ring.Amine oxides of this type are, in particular, C₁₀-C₁₈-alkyldimethylamineoxides and C₈-C₁₂-alkoxyethyldihydroxyethylamine oxides.

Fatty Acid Amides

Fatty acid amides have the formula

where R is an alkyl group having from about 7 to about 21, preferablyfrom about 9 to about 17, carbon atoms, and each R¹ radical is hydrogen,C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl or (C₂H₄O)_(x)H, where x varies fromabout 1 to about 3. Preference is given to C₈-C₂₀-amides,-monoethanolamides, -diethanolamides and -isopropanolamides.

Further suitable nonionic surfactants are, in particular, alkyl andalkenyl oligoglycosides and also fatty acid polyglycol esters or fattyamine polyglycol esters having in each case from 8 to 20, preferablyfrom 12 to 18, carbon atoms in the fatty alkyl radical, alkoxylatedtriglycamides, mixed ethers or mixed formals, fatty acidN-alkylglucamides, protein hydrolyzates, phosphine oxides or dialkylsulfoxides.

Typical examples of amphoteric and zwitterionic surfactants are alkylbetaines, alkylamido betaines, aminopropionates, aminoglycinates, oramphoteric imidazolinium compounds of the formula

where R¹ is C₈-C₂₂-alkyl or -alkenyl, R² is hydrogen or CH₂CO₂M, R³ isCH₂CH₂OH or CH₂CH₂OCH₂CH₂COOM, R⁴ is hydrogen, CH₂CH₂OH or CH₂CH₂COOM, Zis CO₂M or CH₂CO₂M, n is 2 or 3, preferably 2, M is hydrogen or a cationsuch as alkali metal, alkaline earth metal, ammonia or alkanolammonium.

Preferred amphoteric surfactants of this formula are monocarboxylatesand dicarboxylates. Examples thereof are cocoamphocarboxypropionate,cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also calledcocoamphodiacetate) and cocoamphoacetate.

Other preferred amphoteric surfactants are alkyldimethylbetaines andalkyldipolyethoxybetaines containing an alkyl radical, which can belinear or branched, having from about 8 to about 22 carbon atoms,preferably having from 8 to 18 carbon atoms and particularly preferablyhaving from about 12 to about 18 carbon atoms. These compounds aremarketed, for example, by Hoechst AG under the trade name ®Genagen LAB.

Suitable cationic surfactants are substituted or unsubstitutedstraight-chain or branched quaternary ammonium salts of the typeR¹N(CH₃)₃ ^(⊖)X^(⊕), R¹R²N(CH₃)₂ ^(⊖)X^(⊕), R¹R²R³N(CH₃)^(⊖)X^(⊕) orR¹R²R³R⁴N^(⊖)X^(⊕). The radicals R¹, R², R³ and R⁴ may, preferablyindependently of one another, be an unsubstituted alkyl having a chainlength of between 8 and 24 carbon atoms, in particular between 10 and 18carbon atoms, hydroxyalkyl having from about 1 to about 4 carbon atoms,phenyl, C₂- to C₁₈-alkenyl, C₇- to C₂₄-aralkyl, (C₂H₄O)_(x)H, where x isfrom about 1 to about 3, alkyl radicals comprising one or more estergroups, or cyclic quaternary ammonium salts. X is a suitable anion.

The formulations according to the invention comprise, depending on theintended use, as well as said surfactants, also the specific auxiliariesand additives in each case. Thus, for example, detergents and cleanerformulations comprise builders, salts, bleaches, bleach activators,optical brighteners, antiredeposition agents, solubilizers and enzymes.

Customary builders are sodium aluminum silicates (zeolites),phyllosilicates, phosphates, phosphonates, ethylenediaminetetraaceticacid, nitrilotriacetate, citric acid and/or polycarboxylate.

Suitable salts or extenders are, for example, sodium sulfate, sodiumcarbonate or sodium silicate (water glass). Typical individual examplesof other additives which may be mentioned are sodium borate, starch,sucrose, polydextrose, TAED, stilbene compounds, methylcellulose,toluenesulfonate, cumenesulfonate, long-chain soaps, silicones, mixedethers, lipases and proteases.

As well as said surfactants, the cosmetic or pharmaceutical formulationsmay comprise inter alia thickeners, moisturizers, biogenic activeingredients, film formers, conditioners, pearlizing agents,preservatives, perfume or dyes.

Hair shampoos, hair lotions or shower preparations and bath foams maycomprise, as further auxiliaries and additives, emulsifiers such as, forexample, alkoxylated fatty alcohols or sorbitan esters.

The superfatting agents may be substances such as, for example,polyoxyethylated lanolin derivatives, lecithin derivatives and fattyacid alkanolamides, the latter at the same time serving as foamstabilizers.

Examples of suitable thickeners are polysaccharides, in particularxanthan gum, guar, agar agar, alginates and Tyloses,carboxymethylcellulose and hydroxyethylcellulose, also high molecularweight polyethylene glycol mono- and diesters of fatty acids,polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone and alsoelectrolytes such as common salt and ammonium chloride.

Biogenic active substances are taken to mean, for example, plantextracts and vitamin complexes.

Customary film formers are, for example, chitosan, microcrystallinechitosan, quaternized chitosan, polyvinylpyrrolidone,vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acidseries, quaternary cellulose derivatives and similar compounds.

Another component which may be present in the formulation is anonvolatile, liquid silicone. This can either be a polyalkylsiloxane, apolyarylsiloxane, a polyalkylarylsiloxane or a polyethersiloxanecopolymer and is used in an amount of from about 0.1% to about 10.0%,preferably in an amount of from about 0.5% to about 5.0%. Mixtures ofthese liquids can also be used and are also advantageous for certainapplications. The dispersed silicone particles should be insoluble inthe shampoo matrix. The most important nonvolatile polyalkylsiloxaneswhich may be used are, for example, polydimethylsiloxanes havingviscosities of from about 5 to about 600000 centistokes, preferably from350 to about 100000 centistokes, at 25° C. A suitable essentiallynonvolatile polyethersiloxane is, for example, a dimethylpolysiloxanemodified using polypropylene oxide. It is also possible to use startingmaterials containing ethylene oxide and/or propylene oxide.

Suitable silicones are described, for example, in U.S. Pat. No.-2,826,551, U.S. Pat. No. 3,946,500, U.S. Pat. No. 4,364,837 and inGB-849,433.

According to the invention, it is also possible to use silicone gum.Silicone gums are described in U.S. Pat. No. 4,152,416 and in productdata sheets SE 30, SE 33, SE 54 and SE 76 from General Electric.“Silicone gum” is a high molecular weight polydiorganosiloxane having amolar mass of from about 200000 to 1000000. Specific examples arepolydimethylsiloxane, polydimethylsiloxane-methylvinylsiloxanecopolymer, poly(dimethyl-siloxane)-(diphenyl)(methylvinylsiloxane)copolymer and mixtures thereof; mixtures of silicone liquids andsilicone gums are also suitable.

Suitable preservatives are, for example, phenoxyethanol, formaldehydesolution, parabens, pentadiol or sorbic acid.

Suitable pearlizing agents are, for example, glycol distearic acidesters, such as ethylene glycol distearate, but also fatty acidmonoglycol esters.

The dyes which may be used are those substances suitable and approvedfor cosmetic purposes, such as, for example, those listed in thepublication “Kosmetische Färbemittel” [Cosmetic Colorants] from theFarbstoffkommission der Deutschen Forschungsgemeinschaft [DyesCommission of the German Research Society], published by Verlag Chemie,Weinheim, 1984, pp. 81 to 106. These dyes are normally used inconcentrations of from 0.001 to 0.1 % by weight, based on the totalmixture.

The total amount of auxiliaries and additives can be from 1 to 50% byweight, preferably from 5 to 40% by weight, based on thesurfactant-containing formulation.

EXAMPLES

The text below firstly gives a number of guide formulations for a seriesof specific formulations according to the invention. There then followsa number of defined formulations. In all of the examples, DMAP-GA is asugar surfactant of the formula 1 as given above in which Z is a glucoseresidue, R is a C₁₂/C₁₄-fatty acid alkyl radical, unless statedotherwise, and R¹ and R² are in each case methyl. All percentages arepercentages by weight.

Composition Shaving cream 1: Stearic acid 20 to 40% Coconut fatty acid 6to 10% DMAP-GA 1 to 45% Glycerol 5 to 15% Potassium hydroxide 2 to 6%Sodium hydroxide 1 to 3% Plant or mineral oil 1 to 5% Water ad 100%Shaving cream 2: Glycerol monostearate 10 to 35% DMAP-GA 1 to 45%Mineral oil 5 to 15% Glycerol 1 to 10% Water ad 100% Shaving lotion:Cellulose alkyl ether 70 to 75% DMAP-GA 1 to 5% Mineral oil 10 to 20%Glycerol 3 to 10% Water ad 100% Shower gel: Cellulose alkyl ether 5 to10% Na lauryl ether sulfate 2 to 5% DMAP-GA 1 to 45%Cocoylamidopropylbetaine 8 to 15% Ethylene glycol distearate 4 to 10%Isopropyl palmitate 0.5 to 1% Moisturizer 0.25 to 0.5% Preservative 0.05to 0.1% Sodium chloride 3 to 5% Water ad 100% Clear all-purpose cleaner:DMAP-GA 0.1 to 15% Anionic surfactants 0 to 25% Amphoteric surfactants 0to 5% Nonionic surfactants 0.5 to 15% Perfume oil 0 to 1% Preservative 0to 1% Water ad 100% Manual dishwashing detergent: DMAP-GA 0.1 to 15%Anionic surfactants 0 to 40% Amphoteric surfactants 0 to 15% Nonionicsurfactants 0 to 15% Amine oxides 0 to 15% Perfume oil 0 to 1%Preservative 0 to 1% Sodium chloride 0 to 5% Water ad 100% Liquiddetergent: DMAP-GA 0.1 to 15% Anionic surfactants 0 to 40% Nonionicsurfactants 0 to 40% Extenders 0 to 15% Enzymes 0 to 15% Perfume oil 0to 1% Preservative 0 to 1% Dye 0 to 1% Water ad 100%

Example 1

Clear shower gel containing 15% active ingredient (detersivesubstance=DS):

Composition:

A DMAP-GA 4.00% B Water 48.85% C ® Genapol LRO liquid 40.35% PEG 4005.00% Perfume oil 0.30% Preservative q.s. Dye solution q.s. D Citricacid q.s. E Sodium chloride 1.50% Preparation: I Dissolve A in B withwarming II Stir into I the components C one after the other III Regulatethe pH using D, then adjust the viscosity using E

Example 2

Clear shower gel containing 16% active ingredient (DS) without additionof sodium chloride

Composition:

A DMAP-GA 6.00% B Water 54.50% C ® Genapol LRO liquid 30.00% ® GenagenCAB 818 5.00% ® Hostapon KCG 4.00% Perfume oil 0.50% Preservative q.s.Dye solution q.s D Citric acid q.s.

Preparation: As in Example 1

Example 3

Pearlescent shower preparation containing 16% active ingredient (DS)without addition of sodium chloride

Composition:

A DMAP-GA 6.00% B Water 54.70% C ® Genapol LRO liquid 35.00% ® GenapolTSM 4.00% Perfume oil 0.30% Preservative q.s. Dye solution q.s. D Citricacid q.s.

Preparation as in Example 1

Example 4

Clear antidandruff shampoo containing 12.5% active ingredient (DS)without sodium chloride

Composition:

A DMAP-GA 5.00% ® Octopirox 0.50% B Water 64.20% C ® Genapol LRO liquid30.00% Perfume oil 0.30% Preservative q.s. Dye solution q.s. D Citricacid

Preparation as in Example 1

Example 5

Clear antidandruff shampoo containing 12.5% active ingredient (DS):

Composition:

A DMAP-GA 2.50% ® Octopirox 0.50% B Water 57.10% C ® Genapol LRO liquid30.00% ® Medialan LD 6.60% Perfume oil 0.30% Preservative q.s. Dyesolution q.s. D Citric acid q.s. E Sodium chloride 3.00%

Preparation as in Example 1

Example 6

Clear antidandruff shampoo containing 12.5% active ingredient (DS):

Composition:

A DMAP-GA 2.50% ® Octopirox 0.50% B Water 61.35% C ® Genapol LRO liquid30.00% ® Genapol SBE 3.35% Perfume oil 0.30% Preservative q.s. Dyesolution q.s. D Citric acid q.s. E Sodium chloride 2.00%

Preparation as in Example 1

Example 7

Clear hair shampoo containing 15% active ingredient (DS):

Composition:

A DMAP-GA 5.00% B Water 53.70% C ® Genapol LRO liquid 35.00% ® GenapolSBE 5.00% Perfume oil 0.30% Preservative q.s. Dye solution q.s. D Citricacid q.s. E Sodium chloride 1.00%

Preparation as in Example 1

Example 8

Clear all-purpose cleaner containing 10% active ingredient (DS)

Composition:

A DMAP-GA 1.50% B Water 90.70% C ® LRO liquid 1.50% ® Hostapur SAS 606.00% Perfume oil 0.30% Preservative q.s. Dye solution q.s. D Citricacid q.s.

Preparation as in Example 1

Example 9

Clear dishwashing detergent containing 20% active ingredient (DS)

Composition:

A DMAP-GA 2.00% B Water 62.70% C ® Genapol LRO liquid 8.00% ® HostapurSAS 60 25.00% Perfume oil 0.30% Preservative q.s. Dye solution q.s. DCitric acid q.s. E Sodium chloride 2.00%

Preparation as in Example 1

Example 10

Clear dishwashing detergent containing 32.5% active ingredient (DS)without addition of chloride

Composition:

A DMAP-GA 5.00% B Water 53.70% C ® Genapol LRO liquid 6.00% ® HostapurSAS 60 35.00% Perfume oil 0.30% Preservative q.s. Dye solution q.s. DCitric acid q.s.

Preparation as in Example 1

Example 11

Pearlescent shower preparation, 14% DS

Composition:

A ® GENAPOL LRO liquid (Hoechst AG) 35.00% B C12/14-DMAP-GA x lacticacid (Hoechst AG) 7.60% ® GENAPOL PGL (Hoechst AG) 4.00% Perfume oil0.30% Water 53.10% Preservative q.s. Dye solution q.s. C Lactic acidq.s. Preparation I Stir into A the components of B one after the other.II Regulate the pH using C.

Example 12

Clear shower gel, 14% DS

Composition:

A ® GENAPOL LRO liquid (Hoechst AG) 30.00% B C12/14-DMAP-GA xhydrochloric acid 8.40% (Hoechst AG) ® GENAGEN CAB 818 (Hoechst AG)5.00% Perfume oil 0.30% Water 56.30% Preservative q.s. Dye solution q.s.C Hydrochloric acid q.s. Preparation I Stir into A the components of Bone after the other. II Regulate the pH using C.

Example 13

Clear antidandruff shampoo, 14% DS

Composition:

A  ®OCTOPIROX (Hoechst AG) 0.50% B  ®GENAPOL LRO liquid (Hoechst AG)35.00% C C12/14-DMAP-GA x hydrochloric 8.40% acid (Hoechst AG) Perfumeoil 0.30% Water 55.80% Preservative q.s. Dye solution q.s. DHydrochloric acid q.s. Preparation I Dissolve A in B. II Stir into I thecomponents of C one after the other. III Regulate the pH using D.

Example 14

Clear hair shampoo, 14% DS

Composition:

A  ®GENAPOL LRO liquid (Hoechst AG) 35.00% B C12/14-DMAP-GA x lacticacid (Hoechst AG) 7.60% Perfume oil 0.30% Water 57.10% Preservative q.s.Dye solution q.s. C Lactic acid q.s. Preparation I Stir into A thecomponents of B one after the other. II Regulate the pH using C.

Example 15

Universal detergent

Composition: Alkylsulfate 12% Soap 1% Fatty alcohol oxethylate 4%DMAP-GA 3% Sodium carbonate 6% Filosilicate SKS-6 14% Zeolite 14% Sodiumcitrate 5% Sodium sulfate 2% Sodium percarbonate 20% Bleach activator 4%Polyacrylate (CP-5) 6% Enzymes 1% Water ad 100%

Example 16

Light-duty detergent

Composition: Alkylbenzenesulfonate 14% Alkylsulfate 8% Soap 2% Fattyalcohol ethoxylate 4% DMAP-GA 2% Sodium carbonate 1% Filosilicate SKS-65% Zeolite 40% Sodium sulfate 14% Enzymes 1% Water ad 100%

List of commercial products used:

 ®Genapol LRO liquid C₁₂/C₁₈-alkyl diglycol ether sulfate, sodium salt(about 27% DS)  ®Hostapur SAS 60 Secondary alkanesulfonate, sodium salt(about 60% DS)  ®Genapol SBE C₁₂/C₁₈-alkylpolyglycol ethersulfosuccinate, disodium salt (about 40% DS)  ®Medialan LD Fatty acidsarcoside, sodium salt (about 30% DS)  ®Genapol TSM Alkyl ether sulfateand pearlizing agents  ®Genapol OA 080 C₁₂/C₁₄-fatty alcohol ethoxylatecontaining 8 EO  ®Genagen CAB 818 Alkylamidopropylbetaine (about 30% DS) ®Hostapon KCG N-cocoylglutamic acid, monosodium salt (about 25% DS) PEG400 Polyethylene glycol (molar mass about 400)  ®Octopirox1-Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)- 2(1H)pyridinone,2-aminoethanol salt (antidandruff agent)

Performance Investigations

The foaming behavior, the calcium tolerability and the wetting power ofvarious surfactants including DMAP-GA were tested.

1. Foaming Ability

The foaming ability of the following surfactants:

DMAP-GA,

APG (C₁₂/C₁₄-alkyl polyglycoside),

CAPB (C₈/C₁₈-cocoalkylamidopropylbetaine)

was tested using the Ross-Miles method at 37° C. in water with varyingcalcium hardness. The concentration of the surfactants in the water wasin each case 0.3 g/l. In an additional test, 1 ml of grease(Crisco+olive oil, 1:1) was added in each case. The following valueswere measured (foam height in mm):

DMAP-GA APG CAPB 1  0° Gh 140 50 180 2  0° Gh 90 50 70 3  3° Gh 140 20180 4  3° Gh 90 20 80 5 15° Gh 150 20 180 6 15° Gh 110 15 80 7 25° Gh150 20 180 8 25° Gh 80 15 80 (Gh = German hardness)

The results in lines 1, 3, 5 and 7 give the foam height without grease,and the results in lines 2, 4, 6 and 8 give the foam height with theaddition of grease.

Using the same method, DMAP-GA-containing mixtures of the followingcomposition were tested:

I. 1 part of DMAP-GA+4 parts of a mixture of 7 parts of C₁₂/C₁₄-laurylether sulfate+2 EO and 3 parts of C₈/C₁₈-cocoalkylamidopropylbetaine;

II. 1 part of C₁₂/C₁₄-alkyl polyglycoside+4 parts of a mixture of 7parts of C₁₂/C₁₄-lauryl ether sulfate+2 EO and 3 parts ofC₈/C₁₈-cocoalkylamidopropylbetaine.

I II 1  0° Gh 160 175 2  0° Gh 75 40 3  3° Gh 170 180 4  3° Gh 170 145 515° Gh 160 190 6 15° Gh 145 80 7 25° Gh 150 190 8 25° Gh 130 110 (Gh =German hardness)

The results in lines 1, 3, 5 and 7 give the foam height without grease,and the values in lines 2, 4, 6 and 8 give the foam height with theaddition of grease.

In addition, the Ross-Miles foaming ability of the following acidaddition products was measured:

a) C₁₂/C₁₄-DMAP-GA*lactic acid adduct

b) C₁₂/C₁₄-DMAP-GA*HCl adduct

c) C₁₆/C₁₈-DMAP-GA*lactic acid adduct

d) C₁₆/C₁₈-DMAP-GA*HCl adduct

Foam height in mm a) b) c) d) 1.0 250/250 245/245 185/180 190/190 0.1195/195 200/195 160/160 150/145 0.03 35/10 45/15 65/65 80/75 0.006 15/510/5 15/10 25/25 0.002 5/0 5/0 15/10 15/10 Foam volume in ml 1.0 450/440520/510 80/70 130/120

Test conditions: temperature 37° C., water hardness 15°Gh; pH=7

The first number in each case gives the initial measured value, and thesecond number in each case gives the measured value after 5 minutes.

The test results show that the acid adducts also have very good foamingbehavior.

All the figures give the foam height in mm.

The Ross-Miles tests show that DMAP-GA, both as a free amidoamine andalso as an acid adduct, have very good foaming ability alone and also asmixtures of these surfactants with cosurfactants, even in the presenceof grease.

2. Calcium Tolerability

The resistance of the surfactants to hard water was determined bypreparing solutions with increasing concentrations of the surfactanthaving 3 mmol/l, 4.5 mmol/l and 6 mmol/l of calcium hardness and, afternot less than one hour and not more than two hours, observing whetheropalescence or cloudiness have developed or even whether precipitateshave formed. The results are evaluated using the mean of the summedindividual values (5=clear; 4=opalescent; 3=cloudy; 2=slightprecipitation; 1=heavy precipitation).

DMAP-GA C₁₂/C₁₄-glucamide APG CAPB C₁₂-sarcosinate 5 2 3 5 2

The determination of the resistance to hard water shows that thesurfactants and surfactant mixtures according to the invention have verygood calcium tolerability.

3. Wetting Power (DIN ISO 8022)

The immersion wetting power is a measure of the ability of a surfactantsolution to displace air present in a fabric when the fabric is dippedinto the solution. The immersion wetting power of a surfactant isdetermined by determining the wetting time using a cotton swab in asurfactant solution of known concentration.

Surfactant Wetting time (seconds) C₁₂/C₁₄-DMAP-GA *lactic acid 290C₁₂/C₁₄-DMAP-GA *HCl 250 C₁₆/C₁₈-DMAP-GA *lactic acid >300C₁₆/C₁₈-DMAP-GA *HCl >300 DMAP-GA >300 APG 120 GA 100 CAPB 50C₁₂-sarcosinate 40 Na LES 55

The determination of the wetting power shows that the surfactants of theformula 1 and their acid adducts and mixtures of these surfactants withother surfactants have a comparatively long wetting time. This findingis pleasing since good wetting behavior is usually also associated witha strong degreasing action.

The mildness to skin of the surfactants of the formula 1 and their acidadducts and mixtures of these surfactants with other surfactants isconfirmed by determining the zein value and the red blood cell (RBC)value.

For DMAP-GA, a zein value of 39 mg of N/100 ml and an RBC value of 7%denaturation was measured. The values correspond to very good skincompatibility.

What is claimed is:
 1. A surfactant-containing formulation comprising acompound of the formula (1)

where R is an aliphatic radical having from 8 to 24 carbon atoms, R¹ andR², which are identical or different, are alkyl groups having from 1 to4 carbon atoms or hydroxyalkyl groups having from 2 to 4 carbon atoms,and Z is a linear polyhydroxyhydrocarbon radical having at least 3 OHgroups, which may also be alkoxylated, and also its acid additionproducts which additionally comprises one or more anionic, nonionic,cationic and/or amphoteric surfactants—before the period at the end ofthe sentence.
 2. The surfactant-containing formulation as claimed inclaim 1, wherein R¹ and R² are methyl, and Z is the residue of a sugaralcohol derived from a reducing mono- or disaccharide.
 3. Thesurfactant-containing formulation as claimed in claim 2, wherein thereducing monosaccharide is glucose.
 4. The surfactant-containingformulation as claimed in 1, which comprises compounds of the formula(1) in an amount of from 0.1 to 99% by weight.
 5. Thesurfactant-containing formulation as claimed in claim 4, which comprisescompounds of the formula (1) in an amount of from 1 to 50% by weight. 6.The surfactant-containing formulation as claimed in claim 1, in the formof a liquid light-duty detergent, universal detergent, manualdishwashing detergent, rinse aid, liquid cleaner and disinfectant,syndet soap, hair shampoo, hair rinse, hair colorant, hair-wavingcomposition, foam bath, face cleanser, textile and fiber auxiliary,leather fat-liquoring agent, flotation auxiliary and auxiliary forsludge dewatering.